WO2021200794A1

WO2021200794A1 - Active energy ray–curable polyurethane resin, curable resin composition, and production method for active energy ray–curable polyurethane resin

Info

Publication number: WO2021200794A1
Application number: PCT/JP2021/013216
Authority: WO
Inventors: 理紗中原; 正和景岡; 山崎　聡; 士朗山田
Original assignee: 三井化学株式会社
Priority date: 2020-03-30
Filing date: 2021-03-29
Publication date: 2021-10-07
Also published as: JPWO2021200794A1; TW202204463A; JP7324939B2; EP4130085A1; US20230078175A1

Abstract

An active energy ray–curable polyurethane resin that includes a reaction product of a resin raw material that includes an isocyanate group–terminated prepolymer and a hydroxy group–containing unsaturated compound, the isocyanate group–terminated prepolymer including a reaction product of a prepolymer raw material that includes a polyisocyanate component that includes a xylylene diisocyanate and/or a hydrogenated xylylene diisocyanate and a polyol component that includes a polyoxyalkylene polyol that has a number average molecular weight of 6000–12000, and the viscosity of the active energy ray–curable polyurethane resin at 25°C being 20000–40000 mPa·s.

Description

A method for producing an active energy ray-curable polyurethane resin, a curable resin composition, and an active energy ray-curable polyurethane resin.

The present invention relates to an active energy ray-curable polyurethane resin, a curable resin composition, and an active energy ray-curable polyurethane resin.

Polyurethane resin that is cured by irradiation with active energy rays (hereinafter referred to as active energy ray-curable polyurethane resin) is a polyurethane resin containing an ethylenically unsaturated group, and is used in various industrial fields such as adhesives, coating agents, and elastomers. , Widely used.

More specifically, as the active energy ray-curable polyurethane resin, 2,4-tolylene diisocyanate is reacted with polyoxypropylene glycol having a number average molecular weight of 1000, and then 2,4 is added to the obtained reaction solution. -A polyurethane (meth) acrylate oligomer obtained by adding tolylene diisocyanate and 2-hydroxyethyl acrylate and further reacting them has been proposed. It has also been proposed to mix the obtained polyurethane (meth) acrylate with an ethylenically unsaturated compound such as a diacrylate of a bisphenol A / ethylene oxide adduct (for example, Patent Document 1 (Synthesis Example 1)). And Example 1).).

Japanese Unexamined Patent Publication No. 11-315265

On the other hand, as an active energy ray-curable polyurethane resin, further improvement in mechanical strength, weather resistance and hysteresis characteristics after curing is required.

Furthermore, in recent years, it has been studied to use an active energy ray-curable polyurethane resin as a molding resin in a 3D printer.

The molding resin for a 3D printer is required to have a relatively low viscosity before curing, and is required to have excellent mechanical strength, weather resistance and hysteresis characteristics after curing. However, the above polyurethane (meth) acrylate oligomers may not fully satisfy these requirements.

According to the present invention, an active energy ray-curable polyurethane resin, a curable resin composition, and an active energy ray-curable polyurethane having a relatively low viscosity before curing and excellent mechanical strength, weather resistance, and hysteresis characteristics after curing. It is a resin.

The present invention [1] is an active energy ray-curable polyurethane resin containing a reaction product of a resin raw material containing an isocyanate group-terminated prepolymer and a hydroxy group-containing unsaturated compound, and the isocyanate group-terminated prepolymer is xyl. The active energy ray contains a reaction product of a prepolymer raw material containing a polyisocyanate component containing a range isocyanate and / or a hydrogenated xylylene diisocyanate and a polyol component containing a polyoxyalkylene polyol having a number average molecular weight of 6000 or more and 12000 or less. It contains an active energy ray-curable polyurethane resin having a viscosity of the curable polyurethane resin at 25 ° C. of 20,000 mPa · s or more and 40,000 mPa · s or less.

The present invention [2] includes a curable resin composition containing the active energy ray-curable polyurethane resin according to the above [1] and a radically reactive diluent.

The present invention [3] contains the curable resin composition according to the above [2], wherein the radical reactive diluent contains a (meth) acrylate having an alicyclic ether skeleton.

In the present invention [4], a prepolymer raw material containing a polyisocyanate component containing xylylene diisocyanate and / or hydrogenated xylylene diisocyanate and a polyol component containing a polyoxyalkylene polyol having a number average molecular weight of 6000 or more and 12000 or less is reacted. , The step of obtaining the isocyanate group-terminated prepolymer, the step of purifying the isocyanate group-terminated prepolymer by distillation, and reacting the purified isocyanate group-terminated prepolymer with a resin raw material containing a hydroxy group-containing unsaturated compound. Includes a method for producing an active energy ray-curable polyurethane resin, which comprises a step of obtaining an active energy ray-curable polyurethane resin having a viscosity at 25 ° C. of 20,000 mPa · s or more and 40,000 mPa · s or less.

The active energy ray-curable polyurethane resin of the present invention contains a reaction product of an isocyanate group-terminated prepolymer and a hydroxy group-containing unsaturated compound, and the isocyanate group-terminated prepolymer contains xylylene diisocyanate and / or hydrogenated xylylene. A reaction product of a polyisocyanate component containing isocyanate and a polyol component containing a polyoxyalkylene polyol having a number average molecular weight in a predetermined range is contained, and the viscosity of an active energy ray-curable polyurethane resin at 25 ° C. is 20,000 mPa · s. It is 40,000 mPa · s or less.

Therefore, the active energy ray-curable polyurethane resin of the present invention has a relatively low viscosity before curing, and is excellent in mechanical strength, weather resistance, and hysteresis characteristics after curing.

Further, since the curable resin composition of the present invention contains the above-mentioned active energy ray-curable polyurethane resin, the viscosity before curing is relatively low, and the mechanical strength, weather resistance and hysteresis characteristics after curing are excellent.

Further, according to the active energy ray-curable polyurethane resin of the present invention, an active energy ray-curable polyurethane resin having a relatively low viscosity before curing and excellent mechanical strength, weather resistance and hysteresis characteristics after curing can be used efficiently. Can be manufactured well.

The active energy ray-curable polyurethane resin of the present invention is a polyurethane resin that is cured by irradiation with active energy rays (described later).

The active energy ray-curable polyurethane resin contains a reaction product of a resin raw material.

The resin raw material contains an isocyanate group-terminated prepolymer and a hydroxy group-containing unsaturated compound.

The isocyanate group-terminated prepolymer is a polyurethane prepolymer having two or more free isocyanate groups at the molecular ends, and contains a reaction product of a prepolymer raw material.

The prepolymer raw material contains a polyisocyanate component and a polyol component.

The polyisocyanate component contains xylylene diisocyanate and / or hydrogenated xylylene diisocyanate as essential components.

As the xylylene diisocyanate (XDI), 1,2-xylylene diisocyanate (o-XDI), 1,3-xylylene diisocyanate (m-XDI), and 1,4-xylylene diisocyanate (p-XDI) have a structure. Listed as an isomer.

These xylylene diisocyanates can be used alone or in combination of two or more. Examples of the xylylene diisocyanate include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, and more preferably 1,3-xylylene diisocyanate.

As hydrogenated xylylene diisocyanate (also known as bis (isocyanatomethyl) cyclohexane) (H ₆ XDI), 1,2-hydrogenated xylylene diisocyanate (1,2-bis (isocyanatomethyl) cyclohexane, 1,2- H ₆ XDI), 1,3-hydrogenated xylylene diisocyanate (1,3-bis (isocyanatomethyl) cyclohexane, 1,3-H ₆ XDI), 1,4-hydrogenated xylylene diisocyanate (1,4- Bis (isocyanatomethyl) cyclohexane, 1,4-H ₆ XDI) can be mentioned as structural isomers.

These hydrogenated xylylene diisocyanates can be used alone or in combination of two or more. Examples of the hydrogenated xylylene diisocyanate include 1,3-hydrogenated xylylene diisocyanate, 1,4-hydrogenated xylylene diisocyanate, and more preferably 1,3-hydrogenated xylylene diisocyanate.

The xylylene diisocyanate and / or hydrogenated xylylene diisocyanate includes derivatives of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate in addition to the above-mentioned monomers.

Examples of the xylylene diisocyanate and / or a derivative of the hydrogenated xylylene diisocyanate include a multimer (for example, a dimer and / or a trimer of an isocyanurate) of the xylylene diisocyanate and / or a hydrogenated xylylene diisocyanate. Iminooxadiazinedione modified product), pentameric, heptameric, etc.), allophanate modified product (for example, xylylene diisocyanate and / or hydrogenated xylylene diisocyanate, known monovalent alcohol and / or known divalent Alofanate modified product produced by reaction with alcohol), polyol modified product (for example, polyol modified product produced by reaction of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate with known trivalent or higher valent alcohol (alcohol addition) Body), etc.), biuret modified products (eg, xylylene diisocyanate and / or hydrogenated xylylene diisocyanate, biuret modified products produced by reaction with water or amines), urea modified products (eg, xylylene diisocyanate and / Or a urea modified product produced by the reaction of hydrogenated xylylene diisocyanate with diamine), an oxadiazine trione modified product (for example, produced by the reaction of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate with carbon dioxide gas). Oxadiazine trione, etc.), carbodiimide modified product (carbodiimide modified product produced by decarbonation condensation reaction of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate, etc.), uretdione modified product, uretonimine modified product, and the like.

These derivatives can be used alone or in combination of two or more.

Examples of the xylylene diisocyanate and / or hydrogenated xylylene diisocyanate preferably include a monomer of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate, and more preferably hydrogenated xylylene diisocyanate. Examples include 1,3-hydrogenated xylylene diisocyanate.

Further, the polyisocyanate component can contain other polyisocyanates (polyisocyanate excluding xylylene diisocyanate and hydrogenated xylylene diisocyanate) as an optional component.

Examples of other polyisocyanates include aromatic polyisocyanates, aromatic aliphatic polyisocyanates (excluding xylylene diisocyanates), aliphatic polyisocyanates, and alicyclic polyisocyanates (excluding hydrogenated xylylene diisocyanates). Examples include polyisocyanate.

Examples of the aromatic polyisocyanate include tolylene diisocyanate (2,4- or 2,6-toluene diisocyanate or a mixture thereof) (TDI), phenylenediisocyanate (m-, p-phenylenediisocyanate or a mixture thereof), 4, 4'-Diphenyldiisocyanate, 1,5-naphthalenediocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'-or 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI), Examples thereof include aromatic diisocyanates such as 4,4'-toluene diisocyanate (TODI) and 4,4'-diphenyl ether diisocyanate.

Examples of the aromatic aliphatic polyisocyanate (excluding xylylene diisocyanate) include tetramethylxylene diisocyanate (1,3- or 1,4-tetramethylxylene diisocyanate or a mixture thereof) (TMXDI), ω, ω'. -Diisocyanate-1,4-diisocyanate and other aromatic aliphatic diisocyanates can be mentioned.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), and 1 , 5-Pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (also known as hexamethylene diisocyanate) (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6- Examples thereof include aliphatic diisocyanates such as diisocyanate methyl caproate.

Examples of the alicyclic polyisocyanate (excluding hydrogenated xylylene diisocyanate) include 1,3-cyclopentanediisocyanate, 1,3-cyclopentenediisocyanate, and cyclohexanediisocyanate (1,4-cyclohexanediisocyanate, 1,3-cyclohexane). Diisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (also known as isophorone diisocyanate) (IPDI), methylenebis (cyclohexylisocyanate) (also known as bis (isocyanatocyclohexyl) methane) (4,4'- , 2,4'-or 2,2'-methylenebis (cyclohexylisocyanate) These Trans, Trans-form, Trans, Cis-form, Cis, Cis-form, or a mixture thereof) (H ₁₂ MDI), Methylcyclohexanediisocyanate Examples thereof include alicyclic diisocyanates such as (methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate), norbornandiisocyanate (various isomers or mixtures thereof) (NBDI). Preferably, 4,4'-methylenebis (cyclohexylisocyanate) is used.

Other polyisocyanates include derivatives of the same type as above.

Other polyisocyanates can be used alone or in combination of two or more.

When other polyisocyanates (polyisocyanates excluding xylylene diisocyanate and hydrogenated xylylene diisocyanate) are blended, the blending ratio thereof is appropriately selected as long as the excellent effects of the present invention are not impaired.

More specifically, the content ratio of xylylene diisocyanate and hydrogenated xylylene diisocyanate (the total amount thereof when used in combination) is, for example, 50% by mass or more, preferably 50% by mass or more, based on the total amount of the polyisocyanate component. It is 60% by mass or more, more preferably 80% by mass or more, and usually 100% by mass or less.

The polyisocyanate component is preferably composed of xylylene diisocyanate and / or hydrogenated xylylene diisocyanate, and more preferably hydrogenated xylylene diisocyanate.

The polyol component contains a polyoxyalkylene polyol as an essential component.

The polyoxyalkylene polyol is, for example, an addition polymer of alkylene oxide using a low molecular weight polyol or a low molecular weight polyamine as an initiator.

The low molecular weight polyol is a compound having two or more hydroxy groups and having a number average molecular weight of 40 or more and less than 300, and is, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1, 3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol , 3,3-Dimethylol heptane, alcohol (C7-20) diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and mixtures thereof, Dihydric alcohols such as hydride bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol, for example. , Trihydric alcohols such as glycerin, trimethylolpropane, triisopropanolamine, eg tetrahydric alcohols such as tetramethylolmethane (pentaerythritol), diglycerin, eg pentahydric alcohols such as xylitol, eg sorbitol, mannitol, alitol , Hexyl alcohols such as iditol, darsitol, altritor, inositol, dipentaerythritol, for example, heptahydric alcohols such as propylene glycol, for example, octahydric alcohols such as sucrose.

Examples of low molecular weight polyamines include ethylenediamine, 1,3-propanediamine, 1,3- or 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, and 3-aminomethyl-3. , 5,5-trimethylcyclohexylamine (isophoronediamine), 4,4'-dicyclohexylmethanediamine, 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2.1] heptane, 1,3- Low molecular weight diamines such as bis (aminomethyl) cyclohexane, hydrazine, o, m or p-tolylene diamine (TDA, OTD), such as low molecular weight triamines such as diethylenetriamine, such as triethylenetetramine, tetraethylenepentamine, etc. Examples thereof include low molecular weight polyamines having 4 or more amino groups.

These initiators can be used alone or in combination of two or more. Preferred examples of the initiator include low molecular weight polyols.

Examples of the alkylene oxide include ethylene oxide (IUPAC name: oxylan), propylene oxide (1,2-propylene oxide (IUPAC name: methyloxylan)), triethylene oxide (1,3-propylene oxide), butylene oxide (1). , 2-butylene oxide (IUPAC name: ethyloxylane), 2,3-butylene oxide (IUPAC name: 2,3-dimethyloxylan)) and the like. In addition, these alkylene oxides can be used alone or in combination of two or more. Of these, ethylene oxide and propylene oxide are preferable, and propylene oxide is more preferable.

Specific examples of such polyoxyalkylene polyols include average functionalities such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytriethylene glycol, and polyoxyethylene / polyoxypropylene glycol (random or block copolymers). Polyalkylene oxides having 2 groups, for example, polyalkylenes having 3 average functional groups such as polyoxyethylene triol, polyoxypropylene triol, polyoxytriethylene triol, and polyoxyethylene / polyoxypropylene triol (random or block copolymer). Examples include oxides.

These polyoxyalkylene polyols can be used alone or in combination of two or more.

As the polyoxyalkylene polyol, preferably, a polyoxypropylene polyol can be mentioned, and more preferably, a polyoxypropylene glycol can be mentioned.

The number average molecular weight of the polyoxyalkylene polyol is 6000 or more, preferably 7000 or more, more preferably 8000 or more, still more preferably 9000 or more, and particularly preferably 10000, from the viewpoint of mechanical strength, weather resistance and hysteresis characteristics. The above is 12000 or less, preferably 11500 or less, more preferably 11000 or less, still more preferably 10500 or less.

The average number of functional groups of the polyoxyalkylene polyol is, for example, 1.5 or more, preferably 2 or more, for example, 3 or less, preferably 2.5 or less, and more preferably 2.0.

Further, the polyoxyalkylene polyol is produced by a known method using, for example, a hydroxide catalyst, a phosphazene catalyst, a compound metal cyanide complex catalyst, or the like. From the viewpoint of suppressing side reactions, the polyoxyalkylene polyol is preferably produced using a catalyst capable of suppressing side reactions such as a phosphazene catalyst and a compound metal cyanide complex catalyst.

In the side reaction in the production of polyoxyalkylene polyol, monool having an unsaturated bond is produced. Therefore, the degree of suppression of side reactions can be evaluated by calculating the degree of unsaturation (unit: meq./g) of the polyoxyalkylene polyol.

The degree of unsaturation (unit: meq./g) of the polyoxyalkylene polyol preferably satisfies the following formula (1).

Degree of unsaturation ≤ 4 × 10 ^-5 × (Mn / f) ^0.83 + 0.011

In the above formula (1), Mn indicates the number average molecular weight of the polyoxyalkylene polyol, and f indicates the average number of functional groups (average number of hydroxyl groups) of the polyoxyalkylene polyol. Mn and f can be measured by a known method, and can also be calculated from, for example, the hydroxyl value measured according to JIS K1557-1 (2007) (the same applies hereinafter).

More specifically, the degree of unsaturation (unit: meq./g) of the polyoxyalkylene polyol is, for example, 0.001 or more, for example, 0.07 or less, preferably 0.05 or less, more preferably. Is 0.03 or less, more preferably 0.025 or less.

The hydroxyl value of the polyoxyalkylene polyol is, for example, 9 mgKOH / g or more, preferably 10 mgKOH / g or more, and for example, 20 mgKOH / g or less, preferably 15 mgKOH / g or less.

The polyol component can include other high molecular weight polyols (high molecular weight polyols excluding polyoxyethylene glycol) as optional components.

Other high-molecular-weight polyols are compounds having two or more hydroxy groups and having a number average molecular weight of 300 or more and 20000 or less, and are, for example, polyether polyols (excluding polyoxyalkylene polyols), polyester polyols, polycarbonate polyols, and polyurethanes. Examples thereof include polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, silicone polyols, and fluorine polyols. These can be used alone or in combination of two or more. Other high-molecular-weight polyols preferably include polyether polyols (excluding polyoxyalkylene polyols), polyester polyols, polycarbonate polyols, and polyurethane polyols.

Further, the polyol component can contain a low molecular weight polyol as an optional component.

Examples of the low molecular weight polyol include the above-mentioned low molecular weight polyol.

When the polyol component contains a low molecular weight polyol, the content ratio thereof is appropriately set as long as the excellent effect of the present invention is not impaired.

Preferably, the polyol component does not contain a low molecular weight polyol, but contains only a high molecular weight polyol. More preferably, the polyol component contains only a polyoxyalkylene polyol.

The number average molecular weight of the polyol component (total amount) is, for example, 6000 or more, preferably 7000 or more, more preferably 8000 or more, still more preferably 9000 or more, particularly preferably 10000 or more, for example, 12000 or less. It is preferably 11500 or less, more preferably 11000 or less, and even more preferably 10500 or less.

The average number of functional groups of the polyol component (total amount) is, for example, 1.5 or more, preferably 2 or more, for example, 3 or less, preferably 2.5 or less, and more preferably 2.0. Is.

The hydroxyl value of the polyol component (total amount) is, for example, 9 mgKOH / g or more, preferably 10 mgKOH / g or more, and for example, 20 mgKOH / g or less, preferably 15 mgKOH / g or less.

The isocyanate group-terminated prepolymer can be obtained by reacting the prepolymer raw material containing the above polyisocyanate component and the above polyol component by a known method.

More specifically, in this method, the prepolymer raw material is blended at a ratio of more than 1 in the equivalent ratio (isocyanate group / hydroxy group) of the isocyanate group of the polyisocyanate component to the hydroxy group of the polyol component. The equivalent ratio (isocyanate group / hydroxy group) in the prepolymer raw material is preferably 1.1 or more, more preferably 3 or more, still more preferably 6 or more, preferably 20, more preferably 15. Hereinafter, it is more preferably 10 or less.

Then, the above-mentioned prepolymer raw material is reacted by a known polymerization method such as bulk polymerization or solution polymerization. Preferably, the above prepolymer raw materials are reacted by bulk polymerization.

In bulk polymerization, for example, the above prepolymer raw materials are blended in a nitrogen atmosphere and reacted at a reaction temperature of 75 to 85 ° C. for about 1 to 20 hours.

In solution polymerization, for example, in a nitrogen atmosphere, the above prepolymer raw material is mixed with a known organic solvent and reacted at a reaction temperature of 20 to 80 ° C. for about 1 to 20 hours.

Further, in the above polymerization, a known urethanization catalyst can be added if necessary.

The addition ratio of the urethanization catalyst is appropriately set according to the purpose and application.

Thereby, an isocyanate group-terminated prepolymer can be obtained, and as a result, a composition containing an isocyanate group-terminated prepolymer and an unreacted polyisocyanate component (hereinafter referred to as a crude prepolymer product) can be obtained.

The average number of functional groups of the isocyanate group of the isocyanate group-terminated prepolymer is, for example, 1.5 or more, preferably 2.0 or more, and for example, 3.0 or less, preferably 2.5 or less.

The isocyanate group concentration of the prepolymer crude product (including the isocyanate group-terminated prepolymer and the unreacted polyisocyanate component) is, for example, 0. 3% by mass or more, preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and for example, 15% by mass or less, preferably 12% by mass or less, more preferably 10% by mass or more. It is less than or equal to mass%.

In addition, the prepolymer crude product (including the isocyanate group-terminated prepolymer and the unreacted polyisocyanate component) adjusts the viscosity of the active energy ray-curable polyurethane resin at 25 ° C. to the range described below, and is easy to handle and mold. From the viewpoint of improving the properties, it is preferably purified by distillation.

It should be noted that, for example, by setting the equivalent ratio (isocyanate group / hydroxy group) in the prepolymer raw material to a relatively low value without purifying the crude prepolymer product, the temperature of the active energy ray-curable polyurethane resin is 25 ° C. The viscosity of the above can be adjusted within the range described below. However, in such a case, the handleability and moldability may not be sufficient.

Therefore, from the viewpoint of improving handleability and moldability, the prepolymer crude product is preferably purified by distillation, and the viscosity of the active energy ray-curable polyurethane resin at 25 ° C. is adjusted to the range described below.

The distillation method is not particularly limited, and examples thereof include a batch distillation method and a continuous distillation method, and examples of the continuous distillation method include a thin film distillation method (Smith type thin film distillation method). As the distillation method, a thin film distillation method (Smith type thin film distillation method) is preferable.

When the thin film distillation method is adopted, the distillation conditions include, for example, 120 ° C. or higher, preferably 150 ° C. or higher, and for example, 250 ° C. or lower, preferably 200 ° C. or lower. The distillation pressure (absolute pressure) is, for example, 1 Pa or more, preferably 10 Pa or more, more preferably 50 Pa or more, and for example, 300 Pa or less, preferably 200 Pa or less, more preferably 100 Pa or less.

The feed amount of the isocyanate group-terminated prepolymer is, for example, 0.1 g / min or more, preferably 1.0 g / min or more, more preferably 2.0 g / min or more, and for example, 100 g / min. Hereinafter, it is preferably 50 g / min or less, and more preferably 10 g / min or less.

As a result, the unreacted polyisocyanate component is removed from the crude prepolymer product, and a purified product of the isocyanate group-terminated prepolymer (hereinafter referred to as the purified prepolymer) is obtained.

The prepolymer purified product is composed of an isocyanate group-terminated prepolymer, or contains an isocyanate group-terminated prepolymer and a very small amount (10000 ppm or less) of an unreacted polyisocyanate component.

In the prepolymer purified product, the content ratio of the isocyanate group-terminated prepolymer is, for example, 99.5% by mass or more, preferably 99.9% by mass or more, based on the total amount of the prepolymer purified product, for example, 100. It is less than or equal to mass%.

The isocyanate group concentration of the prepolymer purified product is, for example, 0.0001% by mass or more, preferably 0.0005% by mass or more, based on the total amount (solid content equivalent) of the prepolymer purified product. For example, it is 0.020% by mass or less, preferably 0.013% by mass or less, and more preferably 0.010% by mass or less.

Then, an active energy ray-curable polyurethane resin is obtained by reacting the above-mentioned isocyanate group-terminated prepolymer (preferably a purified prepolymer) with a hydroxy group-containing unsaturated compound.

A hydroxy group-containing unsaturated compound is a compound having one or more ethylenically unsaturated groups and one or more hydroxy groups.

More specifically, the hydroxy group-containing unsaturated compound includes, for example, one or more ethylenically unsaturated group-containing groups such as a (meth) acryloyl group, a vinylphenyl group, a propenyl ether group, an allyl ether group, and a vinyl ether group. , It also has one or more hydroxy groups.

In addition, (meth) acryloyl means acryloyl and / or methacrylic acid, similarly, (meth) acrylic means acrylic and / or methacrylic, and (meth) acrylate means acrylate and / or methacrylate. show.

The ethylenically unsaturated group-containing group preferably includes a (meth) acryloyl group, and more preferably an acryloyl group.

When the ethylenically unsaturated group-containing group is a (meth) acryloyl group, examples of the hydroxy group-containing unsaturated compound include hydroxy group-containing (meth) acrylate.

As the hydroxy group-containing (meth) acrylate, for example, a monohydroxymono (meth) acrylate having one hydroxy group in one molecule and one (meth) acryloyl group, for example, a hydroxy group in one molecule. Polyhydroxyl mono (meth) acrylate having a plurality of (meth) acryloyl groups, for example, monohydroxyl poly (meth) having one hydroxy group in one molecule and having a plurality of (meth) acryloyl groups. ) Acrylic, for example, polyhydroxyl poly (meth) acrylate having a plurality of hydroxy groups and a plurality of (meth) acryloyl groups in one molecule.

Examples of the monohydroxyl mono (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 2-. Hydroxyalkyl (meth) acrylates such as phenoxypropyl (meth) acrylate and 4-hydroxycyclohexyl (meth) acrylate, such as 3-chloro-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth). ) Acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethylphthalic acid, 2-hydroxyalkyl (meth) acryloyl phosphate, pentanediol mono (meth) acrylate, neopentyl glycol mono (meth) acrylate, polyethylene glycol mono Examples thereof include (meth) acrylate and polypropylene glycol mono (meth) acrylate.

Examples of the polyhydroxyl mono (meth) acrylate include trimethylolpropane mono (meth) acrylate, glycerin mono (meth) acrylate, and pentaerythritol mono (meth) acrylate.

Examples of the monohydroxyl poly (meth) acrylate include trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and 2-hydroxy-3. -(Meta) acryloyloxypropyl (meth) acrylate (for example, 2-hydroxy-3-acryloyloxypropyl methacrylate (trade name: NK ester 701A, manufactured by Shin-Nakamura Chemical Co., Ltd.)) can be mentioned.

Examples of the polyhydroxyl poly (meth) acrylate include pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, and dipentaerythritol tetra (meth) acrylate.

When the ethylenically unsaturated group-containing group is a vinylphenyl group, examples of the hydroxy group-containing unsaturated compound include 4-vinylphenol, 2-hydroxyethyl-4-vinylphenyl ether, and (2-hydroxypropyl). Examples thereof include -4-vinylphenyl ether, (2,3-dihydroxypropyl) -4-vinylphenyl ether, 4- (2-hydroxyethyl) styrene and the like.

When the ethylenically unsaturated group-containing group is a propenyl ether group, examples of the hydroxy group-containing unsaturated compound include propenyl alcohol, 2-hydroxyethyl propenyl ether, and 2,3-dihydroxypropyl pro. Nenyl ether and the like can be mentioned.

When the ethylenically unsaturated group-containing group is an allyl ether group, examples of the hydroxy group-containing unsaturated compound include allyl alcohol, 2-hydroxyethyl allyl ether, and 2-hydroxypropyl allyl alcohol. And so on.

When the ethylenically unsaturated group-containing group is a vinyl ether group, examples of the hydroxy group-containing unsaturated compound include 2-hydroxyethyl vinyl ether and 2-hydroxypropyl vinyl ether. ..

These hydroxy group-containing unsaturated compounds can be used alone or in combination of two or more.

The hydroxy group-containing unsaturated compound is preferably a hydroxy group-containing (meth) acrylicate, more preferably a monohydroxyl mono (meth) acrylicate, a monohydroxyl poly (meth) acrylate, and even more preferably a monohydroxyl mono. (Meta) acrylates, more preferably hydroxyalkyl (meth) acrylates, and particularly preferably 2-hydroxyethyl (meth) acrylates.

Then, in the reaction between the isocyanate group-terminated prepolymer (preferably the purified isocyanate group-terminated prepolymer) and the hydroxy group-containing unsaturated compound, for example, in an inert gas atmosphere, the above-mentioned isocyanate group-terminated prepolymer is used. The hydroxy group-containing unsaturated compound is blended so as to have a predetermined equivalent ratio, and a urethanization reaction is carried out.

The equivalent ratio (isocyanate group / hydroxy group) of the isocyanate group in the isocyanate group-terminated prepolymer to the hydroxy group in the hydroxy group-containing unsaturated compound is, for example, 0.7 or more, preferably 0.9 or more. For example, it is 1.5 or less, preferably 1.2 or less.

The reaction conditions are not particularly limited, but the reaction temperature is, for example, 40 ° C. or higher, preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and for example, 120 ° C. or lower, preferably 100 ° C. or lower. , More preferably 80 ° C. or lower. The reaction time is, for example, 0.5 hours or more, preferably 1.0 hours or more, and for example, 24 hours or less, preferably 10 hours or less.

Further, in the above reaction, a known urethanization catalyst may be added if necessary. The addition ratio of the urethanization catalyst is appropriately set according to the purpose and application.

As a result, an active energy ray-curable polyurethane resin containing a reaction product of an isocyanate group-terminated prepolymer and a hydroxy group-containing unsaturated compound can be obtained.

More specifically, the active energy ray-curable polyurethane resin is obtained by subjecting the isocyanate group of the isocyanate group-terminated prepolymer and the hydroxy group of the hydroxy group-containing unsaturated compound to a urethanization reaction, and the hydroxy group-containing unsaturated compound. It is a polyurethane resin having an unsaturated bond derived from.

If necessary, the active energy ray-curable polyurethane resin may further include a plasticizer, a blocking inhibitor, a heat-resistant stabilizer, an active energy ray-stabilizing agent (light-resistant stabilizer, etc.), an antioxidant, a mold release agent, and the like. Known additives such as catalysts, pigments, dyes, lubricants, fillers, and antioxidants can be contained in appropriate proportions. The amount of these additives added and the timing of addition are appropriately set according to the purpose and application.

The number average molecular weight of the active energy ray-curable polyurethane resin (standard polystyrene-equivalent molecular weight measured by GPC) is, for example, 5000 or more, preferably 7000 or more, for example, 12000 or less, preferably 11000 or less.

The viscosity of the active energy ray-curable polyurethane resin at 25 ° C. is 20,000 mPa · s or more, preferably 22,000 mPa · s or more, more preferably 22,000 mPa · s or more, from the viewpoint of the tensile strength of the obtained cured product. 24,000 mPa · s or more, more preferably 26,000 mPa · s or more, and from the viewpoint of handleability, 40,000 mPa · s or less, preferably 38,000 mPa · s or less. It is preferably 36,000 mPa · s or less, more preferably 34,000 mPa · s or less, and particularly preferably 32,000 mPa · s or less.

If the viscosity is within the above range, the handleability during molding can be improved.

The viscosity of the active energy ray-curable polyurethane resin is adjusted by purifying the isocyanate group-terminated prepolymer.

Further, the viscosity of the active energy ray-curable polyurethane resin at 25 ° C. is measured by an E-type viscometer according to an example described later.

According to the above-mentioned method for producing an active energy ray-curable polyurethane resin, an active energy ray-curable polyurethane resin having a relatively low viscosity before curing and excellent mechanical strength, weather resistance and hysteresis characteristics after curing can be obtained. , Can be manufactured efficiently.

That is, the above-mentioned active energy ray-curable polyurethane resin contains a reaction product of an isocyanate group-terminated prepolymer and a hydroxy group-containing unsaturated compound, and the isocyanate group-terminated prepolymer contains xylylene diisocyanate and / or hydrogenated xyl. A reaction product of a polyisocyanate component containing a range isocyanate and a polyol component containing a polyoxyalkylene polyol having a number average molecular weight in a predetermined range is contained, and the viscosity of an active energy ray-curable polyurethane resin at 25 ° C. is 20,000 mPa. It is s or more and 40,000 mPa · s or less.

Therefore, the above-mentioned active energy ray-curable polyurethane resin has a relatively low viscosity before curing, and is excellent in mechanical strength, weather resistance, and hysteresis characteristics after curing.

Such an active energy ray-curable polyurethane resin can be used in various industrial fields. More specifically, the active energy ray-curable polyurethane resin can be used as, for example, an adhesive, a coating agent, an elastomer, a molding material, or the like. The active energy ray-curable polyurethane resin is preferably used as a molding material.

Further, when the active energy ray-curable polyurethane resin is used as a molding material, it is preferably used as a mixture (curable resin composition) with a radical-reactive diluent. In such a case, the active energy ray-curable polyurethane resin may be circulated alone and then mixed with a radical-reactive diluent, or the active energy ray-curable polyurethane resin and the radical-reactive diluent may be mixed. It may be distributed as a mixture.

In the present invention, the curable resin composition contains the above-mentioned active energy ray-curable polyurethane resin and a radically reactive diluent.

The radical reactive diluent is a compound that undergoes radical polymerization by irradiation with active energy rays (described later), and is a diluent for diluting the above-mentioned active energy ray-curable polyurethane resin.

Examples of the radical reactive diluent include a reactive compound having an aromatic hydrocarbon skeleton, a reactive compound having an alicyclic hydrocarbon skeleton, a reactive compound having a chain ether skeleton, and an alicyclic ether skeleton. Reactive compounds, reactive compounds with an amide skeleton, reactive compounds with an oxyalkylene skeleton, compounds with (meth) acryloyl groups and vinyl groups, poly (meth) acrylates, unsaturated carboxylic acid allyl esters, the above hydroxy groups. Examples include contained (meth) acrylate.

Examples of the reactive compound having an aromatic hydrocarbon skeleton include (meth) acrylates having an aromatic hydrocarbon skeleton such as 3-phenoxybenzyl (meth) acrylate, such as styrene, vinyltoluene, divinylbenzene, and α-methyl. Examples include styrene.

Examples of the reactive compound having an alicyclic hydrocarbon skeleton include isobornyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, and dicyclopentanyl. Examples thereof include (meth) acrylate having an alicyclic hydrocarbon skeleton such as (meth) acrylate.

Examples of the reactive compound having a chain ether skeleton include 2-ethylhexyl-diglucol (meth) acrylate.

Examples of the reactive compound having an alicyclic ether skeleton include cyclic trimethylolpropane formal (meth) acrylate and (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate. Examples of (meth) acrylates having an alicyclic ether skeleton include 4- (meth) acryloylmorpholine.

Examples of the reactive compound having an amide skeleton include N, N-diethyl (meth) acrylamide and the like.

Examples of the reactive compound having an oxyalkylene skeleton include 2-ethylhexyl-diglycol (meth) acrylate.

Examples of the compound having a (meth) acryloyl group and a vinyl group include methyl 2- (allyloxymethyl) acrylate, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, and (meth). 1-Methyl-2-vinyloxyethyl acrylate, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxy (meth) acrylate Pentyl, (meth) acrylate 6-vinyloxyhexyl, (meth) acrylate 4-vinyloxymethylcyclohexylmethyl, (meth) acrylate p-vinyloxymethylphenylmethyl, (meth) acrylate 2- (vinyloxyethoxy) ) Ethyl, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate and the like.

Examples of the polyol poly (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, pentanediol di (meth) acrylate, and neopentyl glycol di (meth). Polyol di (meth) acrylates such as acrylates, hexanediol di (meth) acrylates, nonanediol di (meth) acrylates, oligoethylene glycol di (meth) acrylates, such as trimethylolpropanthry (meth) acrylates, glycerintri (meth). ) Polypolymer tri (meth) acrylate such as acrylate, for example, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like can be mentioned.

Examples of the unsaturated carboxylic acid allyl ester include allyl (meth) acrylate, diallyl maleate, diallyl fumarate, and diallyl itaconate.

These radical reactive diluents can be used alone or in combination of two or more.

The radical reactive diluent preferably includes a reactive compound having an alicyclic ether skeleton, and more preferably has an alicyclic ether skeleton, from the viewpoint of improving mechanical strength, weather resistance and hysteresis characteristics. (Meta) acrylates are mentioned, more preferably cyclic trimethylolpropane formal (meth) acrylates and (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylates, among others. Preferred are (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylates.

In the curable resin composition, the blending ratio of the active energy ray-curable polyurethane resin and the radically reactive diluent is not particularly limited, and can be used according to the purpose and application as long as the excellent effects of the present invention are not impaired. It is set as appropriate.

More specifically, the active energy ray-curable polyurethane resin is, for example, 40 parts by mass or more, preferably 45 parts by mass, based on 100 parts by mass of the total amount of the active energy ray-curable polyurethane resin and the radical reactive diluent. It is at least 70 parts by mass, for example, 70 parts by mass or less, preferably 65 parts by mass or less. The radical reactive diluent is, for example, 30 parts by mass or more, preferably 35 parts by mass or more, and for example, 60 parts by mass or less, preferably 55 parts by mass or less.

Further, as the radical reactive diluent, preferably, a reactive compound having an alicyclic ether skeleton and a compound having a (meth) acryloyl group and a vinyl group are used in combination. When these are used in combination, the reactive compound having an alicyclic ether skeleton with respect to a total amount of 100 parts by mass of the reactive compound having an alicyclic ether skeleton and the compound having a (meth) acryloyl group and a vinyl group. However, for example, it is 40 parts by mass or more, preferably 45 parts by mass or more, and for example, 99 parts by mass or less, preferably 95 parts by mass or less. The compound containing a (meth) acryloyl group and a vinyl group is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and for example, 60 parts by mass or less, preferably 55 parts by mass or less.

The method of blending the active energy ray-curable polyurethane resin and the radical reactive diluent is not particularly limited, and a known method is adopted. As a result, a curable resin composition is obtained.

Further, the curable resin composition can contain a photopolymerization initiator, if necessary.

Examples of the photopolymerization initiator include known photopolymerization initiators, for example, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-. Benzyl-2- (dimethylamino) -4'-morpholinobtyrophenone, 1,2-octanedione 1- [4- (phenylthio) phenyl] -2- (o-benzoyloxime), etanone-1- [9-ethyl -6- (2-Methylbenzoyl) -9H-Carbazole-3-yl] -1- (O-acetyloxime), 1-hydroxyticlohexyl-phenylketone, 2-hydroxy-2-methyl-1-phenylpropanone And so on.

In addition, the photopolymerization initiator is available as a commercially available product. Examples of such commercially available products include TPO (trade name, manufactured by Tokyo Kasei Kogyo), Irgacure819 (BAPO, trade name, manufactured by BASF), Irgacure369 (Omnirad369, trade name, manufactured by BASF), and IrgacureOXE01 (trade name, manufactured by BASF). ), IrgacureOXE02 (trade name, manufactured by BASF), IrgacureOXE03 (trade name, manufactured by BASF), IrgacureOXE04 (trade name, manufactured by BASF), Irgacure184 (trade name, product name, manufactured by BASF), Omnirad 184, trade name, manufactured by BASF , NCI-831 (trade name, manufactured by ADEKA), NCI-930 (trade name, manufactured by ADEKA) and the like. These can be used alone or in combination of two or more.

The amount of the photopolymerization initiator added is not particularly limited, and is appropriately set according to the purpose and application.

Further, the curable resin composition may contain a known sensitizer or the like, if necessary, in order to promote the photopolymerization reaction by the photopolymerization initiator.

Examples of the sensitizer include 9,10-bis (octanoyloxy) anthracene, 9,10-dibutoxyanthracene, and 1,4-diethoxynaphthalene. These can be used alone or in combination of two or more.

The sensitizer is also available as a commercial product. Examples of such commercially available products include Antracure UVS-581 (trade name, manufactured by Kawasaki Kasei Chemicals), Antracure UVS-1331 (trade name, manufactured by Kawasaki Kasei Chemicals), and Antracure UVS-2171 (trade name, manufactured by Kawasaki Kasei Chemicals). (Made by Kasei Chemicals), etc.

In addition, the curable resin composition, if necessary, is an antioxidant, an ultraviolet absorber, a fluorescent whitening agent, and further, for example, a plasticizer, a blocking inhibitor, a heat stabilizer, an active energy ray stabilizer. Known additives such as (light-resistant stabilizers and the like), mold release agents, catalysts, pigments, dyes, lubricants, fillers, antioxidants and the like can be contained in an appropriate ratio. The amount of these additives added and the timing of addition are appropriately set according to the purpose and application.

Examples of the antioxidant include hindered phenol compounds (specifically, Irganox 1135, Irganox 245, Irganox 1076, Irganox 1726, Irganox 1520L, all manufactured by BASF, specifically ADEKA. ADEKA STAB AO-80 manufactured by BASF Corporation, organic phosphorus compounds (specifically, JP-302, JP-308, JP-308E, JP-310, JP-312L, JP-333E, JP-318O, JPS-312, JPP-13R, JP-318E, all manufactured by Johoku Chemical Co., Ltd., specifically IRGAFOS38, IRGAFOS P-EPQ, all manufactured by BASF, specifically, ADEKA STAB PEP-4C, ADEKA STAB PEP-8, ADEKA STAB 1500 , ADEKA STAB 3010, all manufactured by ADEKA), thioether compounds (specifically, IRGANOX PS800FL, IRGANOX PS802FL, all manufactured by BASF, specifically ADEKA STAB AO-412S, ADEKA STAB AO-503, all ADEKA Examples thereof include Yoshitomi DLTP, Yoshitomi DSTP, Yoshitomi DMTP, all manufactured by API Corporation, and hydroxylamine compounds (specifically, IRGASTAB FS042 manufactured by BASF). These can be used alone or in combination of two or more. The amount and timing of addition of the antioxidant are appropriately set according to the purpose and application.

Examples of the ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2,2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl, and 2- (2'-). Hydroxy-5'-methyl-phenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butyl-phenyl) benzotriazole, 2- (2'-hydroxy-3'-t- Butyl-5'-methyl-phenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di-t-butyl-phenyl) -5-chlorobenzotriazole, 2-( 2'-Hydroxy-4'-n-octoxy-phenyl) Benzotriazole-based UV absorbers such as benzotriazole, such as 2,4-dihydroxy-benzophenone, 2-hydroxy-4-methoxy-benzophenone, 2,2'- Dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sulfobenzophenone, 2-hydroxy-4- Methoxy-2'-carboxy benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxy benzophenone, 2-hydroxy-4-octadesiloxy benzophenone, 2 -Hydroxy-4-n-dodecyloxy-benzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,2', 4,4'-tetrahydroxy-benzophenone, 2-hydroxy-4-dodecyloxy-benzophenone, 2-hydroxy- Benzophenone-based UV absorbers such as 4- (2-hydroxy-3-methacryloxy) propoxybenzophenone, such as 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3-(3'). , 4'-Methylenedioxyphenyl) -acrylate and the like, cyanoacrylate-based ultraviolet absorbers and the like can be mentioned. As commercially available products, for example, Tinuvin328, TinuvinPS (manufactured by Ciba Geigy), SEESORB709 (manufactured by Shiraishi Calcium), Uvinul490 (manufactured by GAF), Permyl B-100 (manufactured by Ferro), Uvinul3035, Uvinul3039, Uvinul3030 (manufactured by Ferro). (Made by BASF) and the like. These can be used alone or in combination of two or more. The amount and timing of addition of the ultraviolet absorber are appropriately set according to the purpose and application.

Examples of the fluorescent whitening agent include 7- (dimethylamino) -4-methylcoumarin, 2,5-bis (5-tert-butyl-2-benzoxazolyl) thiophene, and 4,4'-bis (2). -Benzoxazolyl) Stilbene and the like. Further, as a commercially available product, for example, "TINOPAL OB" (manufactured by BASF) and the like can be mentioned. These can be used alone or in combination of two or more. The amount of the fluorescent whitening agent added and the timing of the addition are appropriately set according to the purpose and application.

Since such a curable resin composition contains the above-mentioned active energy ray-curable polyurethane resin, the viscosity before curing is relatively low, and the mechanical strength, weather resistance and hysteresis characteristics after curing are excellent.

Therefore, the above-mentioned active energy ray-curable polyurethane resin and curable resin composition are suitably used in various industrial fields as, for example, adhesives, coating agents, elastomers, molding materials, and the like. In particular, the above-mentioned active energy ray-curable polyurethane resin and curable resin composition are suitably used as a molding material, more specifically, as a molding material in a 3D printer.

To obtain a molded product (cured product) of the curable resin composition, for example, the curable resin composition is molded into a desired shape and then irradiated with active energy rays to cure the curable resin composition.

Examples of the active energy ray include ultraviolet rays and electron beams. The irradiation amount (integrated light amount) of the active energy ray is, for example, 10 × 10 ^-3 J / cm ² or more, preferably 15 × 10 ^-3 J / cm ² or more, and for example, 6 J / cm ² or less, preferably. Is 5 J / cm ² or less.

Note that the curing by the active energy ray may be a batch curing or a divisional curing. That is, the curable resin composition may be cured by irradiating the active energy ray once, or the curable resin composition may be cured by irradiating the curable resin composition twice or more.

As a result, a molded product (cured product) made of a curable resin composition can be obtained.

Also, after irradiation with active energy rays, it can be cured if necessary.

The curing conditions are not particularly limited, but the temperature conditions are, for example, 10 to 150 ° C, preferably 10 to 100 ° C. The humidity condition is, for example, 20 to 80%, preferably 30 to 70%. The curing time is, for example, 0.5 to 10 days, preferably 1 to 7 days.

Since the obtained molded product (cured product) is obtained by using the above-mentioned active energy ray-curable polyurethane resin having a relatively low viscosity before curing, it is excellent in productivity, and also has mechanical strength, weather resistance and hysteresis. Excellent characteristics.

Next, the present invention will be described based on Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, "part" and "%" are based on mass unless otherwise specified. In addition, specific numerical values such as a compounding ratio (content ratio), a physical property value, and a parameter used in the following description are described in the above-mentioned "mode for carrying out the invention", and the corresponding compounding. Percentage (content ratio), physical property value, parameter, etc. The upper limit value (value defined as "less than" or "less than") or the lower limit value (value defined as "greater than or equal to" or "excess") ) Can be substituted.

Examples 1 to 15 and Comparative Examples 1 to 11

(1) Synthesis of isocyanate group-terminated prepolymer

The isocyanate group-terminated prepolymer was synthesized according to the formulations shown in Tables 1 to 5.

More specifically, according to the formulations shown in Tables 1 to 5, the polyol component was put into a glass separable flask under a nitrogen atmosphere, and then the polyisocyanate component was added to Tables 1 to 5. The mixture was charged at an equivalent ratio (NCO / OH), and then the temperature was raised to 80 ° C.

Then, stannoct (tin (II ethylcaproate)) as a urethanization catalyst was added to the mixture at a ratio of 10 ppm and reacted for 4 hours, whereby the isocyanate group-terminated prepolymer and unreacted poly were added. A crude product containing an isocyanate component was obtained.

(2) Purification of isocyanate group-terminated prepolymer

The crude product containing the isocyanate group-terminated prepolymer is set in a Smith-type thin film distillation apparatus, and the isocyanate group-terminated prepolymer and the unreacted polyisocyanate component are separated under the following conditions to purify the isocyanate group-terminated prepolymer. bottom.

Temperature condition: 160-170 ° C

Pressure condition: 70-100Pa

Supply flow rate: 3.5-4 g / min

In Comparative Example 4, thin film distillation was not performed.

(3) Synthesis of active energy ray-curable polyurethane resin

Purified isocyanate group-terminated prepolymers (prepolymer purified products) are placed in separable flasks in the air (under dry air) according to the formulations shown in Tables 1 to 5, and then hydroxy group-containing unsaturated compounds are added. , The equivalent ratio (NCO / OH) of the isocyanate group of the isocyanate group-terminated prepolymer to the hydroxy group of the hydroxy group-containing unsaturated compound was 1.0, and the temperature was raised to 70 ° C.

Then, stanoct (tin (II ethylhexanoate) as a urethanization catalyst was added to the isocyanate group-terminated prepolymer at a ratio of 200 ppm, and the reaction was carried out for 4 hours until the isocyanate group concentration became 0.01% or less. I let you.

As a result, an active energy ray-curable polyurethane resin was obtained.

Further, the viscosity of the obtained active energy ray-curable polyurethane resin at 25 ° C. was measured on an E-type viscometer (TV25 type viscometer manufactured by Toki Sangyo Co., Ltd., rotor angle: 1 ° 34', rotor radius 2.4 cm). Was measured.

(4) Preparation of curable resin composition

According to the formulations shown in Tables 1 to 5, the active energy ray-curable polyurethane resin, the radical reactive diluent, the photopolymerization initiator, and the additive were put into a brown bottle so as to have a total weight of 100 g. The mixture was stirred at 60 ° C.

As a result, a curable resin composition was obtained.

Further, the viscosity of the obtained curable resin composition at 25 ° C. was measured with an E-type viscometer (TV25 type viscometer manufactured by Toki Sangyo Co., Ltd., rotor angle: 1 ° 34', rotor radius 2.4 cm). bottom.

Since the active energy ray-curable polyurethane resins of Comparative Examples 3, 4 and 6 had high viscosities, they could not be mixed with the radical reactive diluent, and the curable resin composition could not be prepared.

(5) Curing of curable resin composition

The curable resin composition was cured by the methods shown in Tables 1 to 5 to obtain a molded product (cured product).

The curing conditions for each method are shown below.

(A) UV

26 g of the curable resin composition was poured into a polypropylene mold (100 × 100 × 20 mm). Then, under a nitrogen atmosphere, one surface of the curable resin composition was irradiated with UV for 3 minutes with a UV irradiator (M UVBA-0.3 × 0.4 × 0.5 UV405-J manufactured by Aitec System Co., Ltd.). Then, the cured product of the curable resin composition was taken out from the mold, and the other surface was further irradiated with UV for 3 minutes.

(B) High-pressure mercury lamp

・ 26 g of the curable resin composition was poured into a polypropylene mold (100 × 100 × 20 mm). Then, with a high-pressure mercury lamp (high-pressure mercury lamp manufactured by Heleus (custom product)), only one surface of the curable resin composition was irradiated with active energy rays.

The illuminance was set to 630 mW / cm ² (measured with an illuminance meter (UVICURE Plus II (UVA 320 to 390 nm) manufactured by EIT), and the irradiation time was adjusted so that the ^{integrated light intensity was 4 J / cm 2.}

(C) 3D printer

Using a commercially available 3D printer (Phrosen shuffle 4K manufactured by Phrozen), the curable resin composition is cured by irradiation with active energy rays (first curing (precure)), and layers having a film thickness of 100 μm are laminated to 100. A plate of × 50 × 20 mm was obtained. The output of the active energy ray is 0.6 mW / cm ² (measured with a luminometer (measured with a 3664 optical power meter manufactured by Hioki Electric Co., Ltd. (measurement wavelength 405 nm)), and the irradiation time is 90 for the first 10 layers. Seconds, 40 seconds for subsequent layers.

After that, the obtained plate was further cured.

In the second curing (post-cure), a high-pressure mercury lamp (high-pressure mercury lamp manufactured by Heleus (custom product)) was used to irradiate only one surface of the above plate with active energy rays.

<Evaluation>
(1) Mechanical properties

The tensile strength (MPa) and elongation at break (%) of the molded product were measured according to the description of JIS K-6251 (2010).

Further, the tear strength (N / mm) of the molded product was measured according to the description of JIS K-6252 (2007).

(2) Light resistance (weather resistance)

The molded product was subjected to a light resistance test under the following conditions, and the b value difference (Δb value) before and after the test was measured with a color difference meter (Color Ace MODEL TC-1 manufactured by Tokyo Denshoku Co., Ltd.).

Testing machine: Atlas Ci4000

Irradiance: 44 W / m ²

Wavelength range: 300-400 nm

Black panel temperature: 57 ° C

Rain condition: None

Test humidity: no control

Filter (inside / outside): Delight filter

Test time: 40h

(3) Hysteresis loss

Hysteresis (%) of the molded product was measured according to JIS K7312 (1996). The measurement conditions are shown below.

Temperature: 23 ° C

Speed: 0.83 mm / s

Test piece shape: JIS K73121 (1996) No. 3 type

Grab tool distance: 55 mm

Distance between marked lines: 20 mm

Growth: 100%

The details of the abbreviations in the table are shown below.

1,3-H6XDI: 1,3-Hydrogenated xylylene diisocyanate, manufactured by Mitsui Chemicals

IPDI: Isophorone diisocyanate, trade name VESTANAT IPDI, made by Evonik

H12MDI: 4,4'- methylene bis (cyclohexyl isocyanate), the trade name VESTANAT H ₁₂ MDI, manufactured by Evonik

TDI: Mixture of 2,4-tolylene diisocyanate (80%) and 2,6-toluene diisocyanate (20%), trade name TDI-80, manufactured by Mitsui Chemicals

ED-37A: Polyoxyethylene / polyoxypropylene copolymer, average number of functional groups 2, number average molecular weight 3000, degree of unsaturation 0.06 meq. / G, made of Mitsui Chemicals SKC polyurethane

D2000: Polyoxypropylene polyol, average number of functional groups 2, number average molecular weight 2000, degree of unsaturation 0.03 meq. / G, made of Mitsui Chemicals SKC polyurethane

D3000: Polyoxypropylene polyol, average number of functional groups 2, number average molecular weight 3000, degree of unsaturation 0.05 meq. / G, made of Mitsui Chemicals SKC polyurethane

DL4000: Polyoxypropylene polyol, average number of functional groups 2, number average molecular weight 4000, degree of unsaturation 0.01 meq. / G, made of Mitsui Chemicals SKC polyurethane

DL6000: Polyoxypropylene polyol, average number of functional groups 2, number average molecular weight 6000, degree of unsaturation 0.01 meq. / G, made of Mitsui Chemicals SKC polyurethane

DL10000: Polyoxypropylene polyol, average number of functional groups 2, number average molecular weight 10000, degree of unsaturation 0.01 meq. / G, made of Mitsui Chemicals SKC polyurethane

DL12000: Polyoxypropylene polyol, average number of functional groups 2, number average molecular weight 12000, degree of unsaturation 0.02 meq. / G, made of Mitsui Chemicals SKC polyurethane

DL13000: Polyoxypropylene polyol, average number of functional groups 2, number average molecular weight 13000, degree of unsaturation 0.02 meq. / G, made of Mitsui Chemicals SKC polyurethane

HEA: Hydroxyethyl acrylate

IBXA: Radical reactive diluent, isobornyl acrylate, reactive compound with alicyclic hydrocarbon skeleton, manufactured by Osaka Organic Chemical Industry Co., Ltd.

Viscoat 200: Radical reactive diluent, cyclic trimethylolpropane formal acrylate (also known as (5-ethyl-1,3-dioxane-5-yl) methylacrylate), reactive compound with alicyclic ether skeleton, Osaka Organic Made by Chemical Industry

AOMA: Radical reactive diluent, methyl 2- (allyloxymethyl) acrylate, compound with (meth) acryloyl group and vinyl group, manufactured by Nippon Shokubai

FA-513AS: Radical reactive diluent, dicyclopentanyl acrylate, reactive compound having an alicyclic hydrocarbon skeleton, manufactured by Hitachi Kasei

TBCHA: Radical-reactive diluent, 4-tert-butylcyclohexyl acrylate, reactive compound with alicyclic hydrocarbon skeleton, manufactured by KJ Chemicals

DEAA: Radical reactive diluent, N, N-diethylacrylamide, reactive compound with amide skeleton, manufactured by KJ Chemicals

TMPTA: Radical reactive diluent, trimethylolpropane triacrylate, poly (meth) acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.

TPO: Photopolymerization initiator, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, manufactured by Tokyo Chemical Industry Co., Ltd.

Irgacure819: Photopolymerization initiator, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, made by BASF

Irganox 245: Hindered phenolic antioxidant: Ethylene bis (oxyethylene) bis- (3- (5-tert-butyl-4-hydroxy-m-trill) propionate, made by BASF

Example 17
In Example 8, instead of the biscoat 200 in the above table, MEDOL-10 (radical reactive diluent, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate, alicyclic ether A reactive compound having a skeleton, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was blended. As a result, the Δb value of the molded product was improved to 0.7.

Example 18
In Example 1, AOMA was blended in place of the biscoat 200 in the above table. Further, instead of AOMA in the above table, MEDOL-10 was blended. As a result, the breaking strength of the molded product was improved to 9.6 MPa.

Example 19
In Example 1, AOMA was blended in place of the biscoat 200 in the above table. Further, instead of AOMA in the above table, 4HBA (radical reactive diluent, 4-hydroxybutyl acrylate, hydroxy group-containing (meth) acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was blended. As a result, the tear strength of the molded product was improved to 36 N / mm.

Example 20
In Example 8, instead of the biscoat 200 in the above table, ACMO-LI (radical reactive diluent, acryloylmorpholine, reactive compound having an alicyclic ether skeleton, manufactured by KJ Chemicals).

Although the above invention has been provided as an exemplary embodiment of the present invention, this is merely an example and should not be construed in a limited manner. Modifications of the present invention that will be apparent to those skilled in the art are included in the claims described below.

The active energy ray-curable polyurethane resin, the curable resin composition, and the active energy ray-curable polyurethane resin of the present invention are preferably used in, for example, adhesives, coating agents, elastomers and molding materials.

Claims

An active energy ray-curable polyurethane resin containing a reaction product of a resin raw material containing an isocyanate group-terminated prepolymer and a hydroxy group-containing unsaturated compound.
The isocyanate group-terminated prepolymer is
Polyisocyanate components, including xylylene diisocyanates and / or hydrogenated xylylene diisocyanates,
It contains a reaction product of a prepolymer raw material containing a polyol component containing a polyoxyalkylene polyol having a number average molecular weight of 6000 or more and 12000 or less.
An active energy ray-curable polyurethane resin characterized in that the viscosity of the active energy ray-curable polyurethane resin at 25 ° C. is 20,000 mPa · s or more and 40,000 mPa · s or less.
The active energy ray-curable polyurethane resin according to claim 1 and
A curable resin composition comprising a radical reactive diluent.
The curable resin composition according to claim 2, wherein the radical-reactive diluent contains a (meth) acrylate having an alicyclic ether skeleton.
A prepolymer raw material containing a polyisocyanate component containing xylylene diisocyanate and / or hydrogenated xylylene diisocyanate and a polyol component containing a polyoxyalkylene polyol having a number average molecular weight of 6000 or more and 12000 or less is reacted to obtain an isocyanate group-terminated prepolymer. The process of obtaining and
A step of purifying the isocyanate group-terminated prepolymer by distillation, and
An active energy ray-curable polyurethane resin having a viscosity at 25 ° C. of 20,000 mPa · s or more and 40,000 mPa · s or less by reacting a resin raw material containing the purified isocyanate group-terminated prepolymer with a hydroxy group-containing unsaturated compound. A method for producing an active energy ray-curable polyurethane resin, which comprises a step of obtaining an active energy ray-curable polyurethane resin.